US3012305A - Electrically unsymmetrically conductive system and method for producing same - Google Patents

Electrically unsymmetrically conductive system and method for producing same Download PDF

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US3012305A
US3012305A US664358A US66435857A US3012305A US 3012305 A US3012305 A US 3012305A US 664358 A US664358 A US 664358A US 66435857 A US66435857 A US 66435857A US 3012305 A US3012305 A US 3012305A
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Ginsbach Karl-Heinz
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Licentia Patent Verwaltungs GmbH
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof  ; Multistep manufacturing processes therefor
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C30B15/20—Controlling or regulating
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B31/00—Diffusion or doping processes for single crystals or homogeneous polycrystalline material with defined structure; Apparatus therefor
    • C30B31/06—Diffusion or doping processes for single crystals or homogeneous polycrystalline material with defined structure; Apparatus therefor by contacting with diffusion material in the gaseous state
    • C30B31/18—Controlling or regulating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
    • H01L21/228—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities using diffusion into or out of a solid from or into a liquid phase, e.g. alloy diffusion processes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/24—Alloying of impurity materials, e.g. doping materials, electrode materials, with a semiconductor body
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof  ; Multistep manufacturing processes therefor
    • H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
    • H01L29/36—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the concentration or distribution of impurities in the bulk material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S438/00—Semiconductor device manufacturing: process
    • Y10S438/965—Shaped junction formation

Definitions

  • This invention relates to electrically unsymmetrically conductive systems and a method for producing the same. It relates more particularly to a new type of dry plate rectifier of semi-conductive material and a method for its manufacture.
  • the semi-conductive materials used in the art of manufacturing electrically unsymmetrically conductive systems have been principally germanium, silicon, and intermetallic compounds between metals of the groups 1H and V of the periodic table.
  • These semi-conductive materials are distinguished from other semi-conductive substances such as selenium or cupreous oxide, by the fact that they can support much greater current loads and show substantially higher barrier potentials, and are therefore preferably employed in the construction of high power current rectifiers.
  • An ideal high power current rectifier must preferably consist of a semi-conductor body having a p-n junction of the most favorable properties of a high current flow therethrough, and simultaneously have a very high barrier potential.
  • Such semi-conductor bodies have thus far not been manufactured in the art.
  • a second known process for obtaining p-n junctions is that of applying to the surface of a semi-conductor body a material of opposite conductivity type and heating this material and theadjacent zone of the semi-conductor body sufficiently to cause diffusion of charged particles of the material into the semieconductor body.
  • the resulting p-n junctions are broad ones, having a flat gradient from the center of the junction toward the adjacent zones of the semi-conductor body, and their properties are correspondingly very satisfactory with regard to their barrier potential, but unsatisfactory with regard to their high resistivity to heavy current loads.
  • the same diffusion effect may also be obtained by contacting a semi-conductor crystal with the gaseous phase of a substance imparting to the crystal an opposite conductivity type and heating so that diffusion takes place into the semi-conductor crystal directly from the gaseous phase.
  • the resulting p-n junction sufiers from the same drawbacks as when applying a coating according to the aforesaid second known process and thus causing dilfusion by heating from a superimposed solid phase into the semi-conductor crystal.
  • the barrier layer breaks down at a certain limit barrier voltage, preferably in the region where the p-n junction emerges at the crystal surface. It is believed that this is due to the fact that it is impossible to maintain this surface of the semi-conductor crystal entirely free from undesirable impurities. I have found that the narrower the 31-11 junction, the more sensitive it is against such impurities, and the more readily does it break down along the crystal surface.
  • the resulting semiconductor crystals have a flattened gradient of their p-n junction in the vicinity of the crystal surface and are said to be particularly Well suited as material for diodes.
  • My invention avoids the above-described diificulties and draw-backs and attains the objects stated hereinbefore, by providing a new type of dry plate rectifying system and a novel process for manufacturing the same which combines the known method of obtaining narrow p-n junction having a steep gradient of impurity distribution of the opposite conductivity type, which method is known as falloying method and is, for instance, described in detail in US. Patent 2,725,315 granted to C. S. Fuller November 29, 1955, with other steps known ,per so which have also been described above.
  • This simple and easily controllable method permits to obtain a semi-conductive system which combines the advantageous features of firstly excellent current flow properties in the direction of the forward current, and
  • the p-n junction is made narrow over substantially the entire extension thereof except in a relatively small marginal portion which is retained at its original breadth, so as to obtain the necessary high current flow in the direction of the forward current.
  • FIGURE 1 illustrates graphically the gradient of impurity distribution of a uniform p-n junction in a conventional semi-conductor crystal
  • FIGURE 2 illustrates in perspective and partially sectional view a semi-conductive system having a p-n junction according to the invention
  • FIGURE .3 shows graphically the characteristics of the p-n junction in the interior and at the surface of the semi-conductive system of FIGURE 2;
  • FIGURE 4 illustrates perspectively and partly in section another embodiment of a semi-conductive system according to the invention similar to that shown in FIG- URE 2;
  • FIGURE 5 illustrates a dry plate rectifier comprising a semi-conductive system according to the invention
  • FIGURE 6 (a to 1) illustrates, by way of example one mode of carrying out the process of making a semiconductor system according to the invention
  • FIGURE 7 (a to 1) illustrates, by way of example another mode of carrying out the process of manufacturing a semi-conductor system according to the invention.
  • the semi-conductor crystal 1 consists of an n-conductivity type portion 1,, and a p-conductivity type portion 1;, which are ideally divided by the central plane I of the junction between both portions 1, and 1
  • a coordinate system has been placed in the longitudinal central plane of the crystal 1, with the ordinate axis being located in the plane I of the p-n junction and being subdivided in units of concentration N of impurities being either donors or acceptors, i.e. contributing to imparting either nor p-conductivity type to the crystal 1.
  • the abscissa is subdivided into units of length starting from the ordinate as towards both ends of crystal 1.
  • the concentration N of donors is high while the concentration N of acceptors is low, the excess of donors determining the conductivity type of this portion as It. From a certain region, N decreases at a gradient characterized by a to a low level, while N rises at a gradient 6 to a high level, thereby reversing the conductivity type on the left, side of J, in which the concentration of acceptors now exceeds that of donors.
  • the steeper angles a and 9 i.e. the gradients of concentrations of donors and acceptors, the narrower is the extension of the entire transition region a, which constitutes the p-n junction, and invertedly, the flatter these gradients, the broader is the junction.
  • the semi-conductive system of a dry plate rectifier illustrated schematically in'the sectional view of FIG- URE 2 comprises a semi-conductor crystal 1 which consists of an n-conductive portion 2 and a p-conductive portion 3, while the p-n junction extends between limits 4 and and emerges at the surface 1a of crystal 1 in a belt zone whose central plane intersects surface 1a as indicated at 6.
  • the gradient of the concentration of impurities of either por n-type, as the case may be, is flatter as is indicated by angles a' and B in FIGURE 3, while, in the central portion of the p-n junction which extends over almost the entire cross sectional area of the crystal 1 in the plane 6, this gradient is steeper as indicated by angles a" and ,8" in FIGURE 3-.
  • the 13-11 junction has a diameter b, while in the marginal portions thereor, its diameter is approximately 0.
  • the marginal zone 8 having a flat gradient of impurity concentration is nnsy'mmetrically disposed relative to the central plane 9 of the p-n junction 14) tending through the semi-conductor crystal 11,
  • FIGURE 5 there isillustrated a dry plate rectifier system of the invention, which comprises a semi-conductor disc 2% of, for instance, p-type conductive germanium or silicon, an n-type semi-conductive alloy body 21 and therebetween a p-n junction which has a broad marginal portion 22 and a narrowed central portion 23.
  • a dry plate rectifier system of the invention which comprises a semi-conductor disc 2% of, for instance, p-type conductive germanium or silicon, an n-type semi-conductive alloy body 21 and therebetween a p-n junction which has a broad marginal portion 22 and a narrowed central portion 23.
  • the alloy body 21 consists of a portion of n-type germanium or silicon, containing gallium or indium or their intermetallic compounds such as gallium arsenide or indium antimonide, and/0r alloyed with lithium, or tin or gold containing, for instance, antimony or arsenic.
  • Elements of the third group of the periodic table, other than gallium or indium, namely boron, aluminum, and thallium are also suitable for forming the alloy layer 23. with n-type or p-type germanium or silicon, as shall be described hereinafter.
  • the dry plate rectifier system shown in FIGURE 5 further comprises a base plate 24 of preferably molybdenum on which the semi-conductor disc 2 is mounted free from barrier layers, for instance, with a solder layer 25 of tin, or tin-antimony or tin-indium, as the case may be.
  • Electrode 26 of aluminum is welded to the top of alloy body 21,'while electrode 27, for instance of copper, is welded to the molybdenum base plate 24.
  • a dry plate rectifier of this type is manufactured by the method according to the invention of which several modes are illustrated in FIGURES 6 and 7.
  • FIGURE 6 illustrates as a preferred mode of the method of making dry plate rectifier systems according to the invention, a step (a) of drawing from a melt of either germanium or silicon containing donor and acceptor substances, a monocrystal in which a relatively broad p-n junction is conventionally produced by changing at a determined time, the growth rate of the crystal.
  • the conductivity type of a drawn germanium monocrystal is changed from n-type to p type conductivity, thus leading to a monocrystal as illustrated by (b) in FIGURE 6, which crystal consists of the p-type conductivity portion 13, the n-type conductivity portion 14, and the p-n junction 15 which is relatively broad on both sides of the central plane 16 thereof.
  • a pellet or small disc 17 is placed on top of one of the end surfaces of the monocrystal.
  • This pellet is of a substance which imparts the same type of conductivity to the semi-conductor body, as prevails in the crystal portion on whose surface it is placed.
  • pellet 17 is placed on the top surface of crystal portion 13 which is of p-type conductivity. Consequently, pellet 17 is of an element from the third group of the periodic table comprising boron (as a metaloid), and the metals aluminum, gallium, indium and thallium.
  • a layer of one of the aforesaid substances may be deposited on the surface of portion 13 from the vapor phase.
  • FIG- URE 6 That part of the crystal surface which is not to be coated, is preferably covered by a mask 18 (FIGURE 6 (d)).
  • step (e) FIGURE 6 the entire system of FIGURE 6 (d) is heated in an inert atmosphere, for instance of argon or another suitable gas, during a few seconds to a temperature above 500 3. so as to melt the pellet 17 and alloy the same with the p-conductive portion 13 of the semi-conductor monocrystal.
  • p-conductivity type impurities penetrate into the barrier layer zone and reduce the width of the p-n junction to a range of 1 micron and less, down to about 0.1 micron. This narrowing of the p-n junction zone is due to the alloying melting of the pconductive crystal portion 13 down into the zone of the p-n junction 15 in that part of portion 13 which lies below pellet i7.
  • Pellet 17 and portion 13 are thus fused together to form a combined p-conductive portion 19, and a semi-conductive system as illustrated in FIG- URE 6 (f) is obtained.
  • the p-n junction is narrowed in its central portion 15 but broad in its marginal portion 15'.
  • a given conductivity type semi-conductor crystal of silicon, germanium, or an intermetallic compound of a metal of the third subgroup with a metal of the fifth subgroup of the periodic table is provided with a p-n junction by the heat difiusion known per se (FlGURE 7a and b).
  • a semi-conductor block (FIGURE 70) comprising a pn junction -49, a p-conductive layer 41 and an n-conductive crystal portion 42 is then cut out of the diffusion treated semi-conductor body shown in FIGURE 76.
  • a pellet is placed on that surface of the block, next to which there is located the p-n junction, and is alloyed thereto in the above-described manner, or a layer of 1a corresponding substance is vapor-deposited on that surface andheat alloyed thereto (FlGURE 7(d, e,) or 2 2))-
  • the resulting semi-conductor system (FIGURE 7 is similar to that shown in FIGURE 6
  • the first described mode of ope ation (FEGURE 6(a, b, c d, e, f)) is the preferred mode because it is the best mode of controlling the final thickness of the p-n junction in the area of narrowed diameter.
  • My invention shall be further illustrated by a number of examples describing how the same can be carried out in practice, which examples shall, however, be considered in no way as lim-itative thereof.
  • Example I A monocrystal of germanium is drawn first at a growth rate of l millimeter per minute and then at 3 millimeters per minute from a melt containing germanium and, as impurity materials, gallium and arsenic. Thereby, the initially n-type conductive monocrystal changes its character to p-type conductivity.
  • the crystal can be drawn, for instance, to a size of 9.5 m'llimeter thickness and 15 millimeters diameter.
  • a pellet of indium metal having a diameter of about 10 millimeters is then placed on the p-ty c germanium surface.
  • the system is then heated for seconds under argon to about 500 C., i.e. below the melting point of germanium (936 C.).
  • the p-n junction whose initial thickless is approximately 1 to 10 microns, is narrowed in the area covered by the pellet to a thickness of, for instance, about 0.8 micron or less.
  • a copper electrode of about 8 millimeters diameter is then welded on to the molybdenum layer, and an aluminum wire of about the same diameter of 8 millimeters is welded on to the alloyed indium-p-type germanium surface of the semi-conductor system.
  • the dry plate rectifier thus obtained supports a current load of about 250 amperes per square centimeter and a barrier voltage of about 690 volts. 7
  • Comparable known semi-conductive systems comprising drawn germanium monocrystals support either barrier voltages up to 400 volts and very low current loads in the order of milliamperes up to a few amperes per Cm.
  • Dry plate rectifiers manufactured according to Example l and the following examples are particularly distinguished by their property of supporting increased pulse loads.
  • Example I A germanium monocrystal of partly p-type and partly n-type conductivity and having a p--n junction intermediate these parts is prepared in the same manner as described in Example l, but mounted on the molybdenum base plate with it's p-type conductivity surface instead of its n-type conductivity side, which mounting with the p-type conductivit" surface to the molybdenum base plate is effected by means of an indium solder.
  • Example II A pellet of tin containing about 8.5% of arsenic is used instead of the indium pellet described in Example 1. Otherwise, the steps of Example I are followed.
  • Example III A monocrystal of silicon is drawn first at a growth rate of 1.2 millimeters per minute, and then, after a given period, at the rate of 3.5 millimeters per minute from a melt containing silicon and, as impurity materials, lithium and an aluminum arsenic compound.
  • the resulting semi-conductive crystal has a p-type conductivity portion, a 12-11 junction and an n type conductivity portion, and may be grown, for instance, to a thickness of 0.25
  • the crystal is then mounted with its p-side on a molybdenum base plate having a diameter of, for instance, 22 mm., with the aid of an indium tin alloy solder containing about 25% of indium.
  • a pellet having a diameter of about 12 mm. and consisting of tin containing about 0.5% of arsenic is then placed on the top surface of the n-type conductive silicon portion, and the system is then heated to 800 C. for about 10 seconds.
  • the 33-12 junction is thereby narrowed in its central region to a width of about 1 micron.
  • An aluminum electrode is then welded to the alloyed side of the system, and a copper electrode to the molybdenum base plate. Both electrodes have diameters of about 10 mm.
  • the resulting electrically nnsymmetrically conductive system can be used as a dry plate rectifier which Withstands current loads of 300 amperes per cm. and a barrier voltage of about 950 volts.
  • Example I V A semi-conductive crystal is obtained by the steps described in Example Ill. Instead of mounting the crystal with its p-side on the molybdenum base plate, the crystal is mounted with its n-side on a molybdenum base plate having a diameter of, for instance, 22 mm, with the aid of a tin arsenic alloy solder containing about 0.5% of arsenic.
  • a pellet having a diameter of about 12 mm. and consisting of aluminum containing approximately 50% of indium is then placed on the top surface of the p-type conductive silicon portion. All other steps are the same as described in Example llIl.
  • Example V A p-type conductive germanium disc having a thickness of about 0.5 mm. and a diameter of about 14 mm., and whose resistivity is about 1 ohm centimeter is blanched and then covered with a molybdenum mask which leaves a circular surface portion of one fiat side of the disc free; the diameter of the free surface is about 11 mm.
  • a lithium metal layer having a thickness of 0.1 mm. is then vapor deposited in vacuum on to this free portion of the disc surface.
  • the system is then heated in a helium atmosphere for about 10 seconds to about 700 C. whereby a p-n junction is formed at a depth of about 0.1 mm. below the lithium coated surface.
  • Lithium-germanium alloy which may have formed during the heating step as well as excessive lithium are then removed mechanically.
  • the semi-conductive system according to the invention is then produced by again covering the surface into which the p-n junction has been difiused, with a molybdenum mask having a central opening of 10 mm. diameter, and vapor depositing thereinto a layer of tin-antimony alloy containing about 0.5% of antimony, which layer is about 1.2 mm. thick.
  • the alloying step is then carried out by heating the system to about 500 C. for 15 seconds in an argon atmosphere.
  • the p-n junction is narrowed in the area registering with the tin antimony deposit to a thickness below 0.8 micron.
  • the p-type surface of the system is soldered to a molybdenum plate by means of indium.
  • the system is then electrolytically blanched in a 10% kalium hydroxide solution and then rinsed in distilled water.
  • Example VI below the lithium bearing surface.
  • the further treatment is similar to that described in the preceding example.
  • mony content of about 5% is used as the alloying substance, and the alloying step is carried out during 8 seconds at a temperature of 800 C.
  • the p-type surface is soldered to a molybdenum plate by an indium aluminum alloy containing about 50% of indium.
  • Example VII gold having an anti-' A block of n-type conductive silicon having a resistivity of about 2 ohm-cm, is blanched in a conventional manner and then heated during 16 hours at l200'C. in an inert atmosphere, for instance helium, containing about 1 percent by volume of boron triiodide B1 and having a pressure of about 300 Torr at 20 C.
  • an inert atmosphere for instance helium
  • a disc-shaped section as illustrated in FIGURE 7b and having a thickness of 0.3 mm. is cut from the block.
  • Example V an aluminum layer having a thickness of 0.1 mm. is then vapor deposited on the p-type conductive surface of the disc, whereupon the system is heated for about 7 seconds at 900 C. so as to alloy the aluminum and the p-type conductive boron-containing silicon.
  • Intermetallic compounds such as gallium phosphide, gallium arsenide, indium antimonide and others formed between elements of the third and fifth group of the periodic table, ie between the elements Al, Ga, In, Te on the one hand and the elements P, As, Sb, Bi on the other hand may also be provided with p-n junctions in a conventional manner and then subjected to the alloying treatment according to my invention, with suitable substances, in the manner described in the preceding examples.
  • a method for producing an electrically unsymmetrically conductive system comprising a body of semiconductive material of a given type conductivity selected from the group consisting of silicon, germanium and fusible intermetallic compounds, which method comp-rises the steps of (a) producing a mono-crystal semi-conductive body having a p-n junction, said p-n junction thus having a given gradient of impurity concentrations of donors and acceptors changing substantially evenly in a direction vertically to'the extension of the junction over the entire area of the latter, and (b) of causing impurities to diffuse into a central portion of said p-n junction so as to increase said gradient therein, while (0) preventing a change of said gradient in the remaining portion of said p-n junction.
  • the method producing a semi-conductor diode comprising the steps of (a) producing a semi-conductor body having two portions of opposite conductivity types and a p-n junction extending over the entire area between said portions, (12) applying to a limited surface area of one of said portions, which surface area is substantially parallel with said p-n junction, and smaller than the entire area of the latter, a material imparting to said semiconductor body the same conductivity type as that of the body portion to a surface area of which said material is being applied, and (c) heating the body and material sutficiently to alloy the latter with the body portion to which it is applied and thereby to reduce the thickness of the p-n junction in a central are-a substantially equal in extension to said limited surface area.
  • a method for producing an electrically unsymmetrically conductive system capable of supporting high current loads at high barrier voltages comprising the steps of producing in a semi-conductor body of n-type conductivity a portion of p-type conductivity and a p-n junction between said portion of p-type conductivity and the remaining portion of said n-type body by drawing a monocrystal of silicon from a'melt containing silicon and impurity material composed of lithium and an aluminumarsenic compound and changing the growth rate thereof at a determined instant; placing a pellet of aluminum containing 50% of indium metal upon the surface of said p-type silicon portion, said pellet being smaller than said latter surface; heating said system under argon to a temperature below the melt-ing point of silicon, thus causing alloying of said indium metal and that part of said p-type silicon portion underlying said pellet of indium and causing difiusion of said indium into a central portion of said p-n junction so as to reduce the thickness of the latter in the interior of the system
  • a method for producing an electrically unsymmetrically conductive system capable of supporting high current loads at high barrier voltages comprisin the steps of blanching a block of n-type conductivity silicon, heating said block in helium containing 1% of boron triiodide thus causing the boron to be diffused into said block thereby forming a p-n junction, cutting a disc-shaped section from said block so as to expose said junction at the surface of said section, vapor depositing an aluminum layer upon a limited, circular central portion of the p-type conductivity surface of said disc while leaving uncovered a marginal portion of said p-type conductivity surface, heating said disc so as to alloy said aluminum and said p-type conductive boron-containing silicon-so as to reduce the thickness of said p-n junction in the interior of the system below said central portion while retaining the original thickness of the p-n junction where the same emerges at the surface of the system and below said marginal portion, and mounting the system with its n-type surface on a molyb
  • a method of producing a semiconductor diode comprising the steps of:
  • the method of producing a semiconductor diode comprising the steps of: producing a semiconductive disc having two portions of opposite conductivity types and a p-n junction extending over the entire area between said portions; covering said disc with a mask leaving free a limited central surface area pertaining to the surface of one of said disc portions; depositing a substance on said surface area left free by said mask, said substance imparting to said disc portion to which it is applied the same type of conductivity as already present therein; and heating said disc and causing said substance to diffuse into a central portion of said p-n junction so as to reduce the thickness thereof in said central portion while the thickness of the remaining portion of said p-n junction remains substantially unaffected thereby.

Description

Dec. 12, 1961 KARL-HEINZ GINSBACH 3,012,305
ELECTRICALLY UNSYMMETRICALLY CQNDUCTIVE SYSTEM AND METHOD FOR PRODUCING SAME Filed June 7, 1957 3 Sheets-Sheet 1 l I I l i l p-semicondud maferl'al Attorneys nited rates atent animus Fatented Dec. 12, 1951 3 012 305 ELECTRECALLY UNSMIETRICALLY CONDUC- TWE SYSTEM AND METHOD FGR PRSDUCZNG SAD/ E Karl-Heinz Ginsbach, Warstein, Germany, assignor to Licentia PatenhVerwaltungs-Gan.b.H., Hamburg, Germany Filed June 7, 1957, her. No. 664,358 Claims priority, application Germany June 7, E56 '7 Cimms. (Cl. 29-253) This invention relates to electrically unsymmetrically conductive systems and a method for producing the same. It relates more particularly to a new type of dry plate rectifier of semi-conductive material and a method for its manufacture.
it is an object of my invention to provide an electrically unsymmetrically conductive system which is particularly suitable for use as a dry plate rectifier for high power conversion and a method for its manufacture.
it is another object of my invention to provide an electrically semi-conductive system of the aforesaid type which is capable of supporting high barrier voltages without breakdown, while, at the same time, permitting the flow of high power currents through the system which thus serves as a rectifier.
Recently, the semi-conductive materials used in the art of manufacturing electrically unsymmetrically conductive systems, and in particular dry-plate rectifying devices, have been principally germanium, silicon, and intermetallic compounds between metals of the groups 1H and V of the periodic table.
These semi-conductive materials are distinguished from other semi-conductive substances such as selenium or cupreous oxide, by the fact that they can support much greater current loads and show substantially higher barrier potentials, and are therefore preferably employed in the construction of high power current rectifiers.
Particularly interesting in this respect are those substances in which the rectifying efiect is achieved at a p-n junction provided in a monocrystal semi-conductor body.
An ideal high power current rectifier must preferably consist of a semi-conductor body having a p-n junction of the most favorable properties of a high current flow therethrough, and simultaneously have a very high barrier potential. Such semi-conductor bodies have thus far not been manufactured in the art.
One known process by means of which p-n junctions are obtained in semi-conductor monocrystals is that of growing them with the aid of a seed crystal from a melt. This process is described in detail in the British Patent 738,231 granted to General Electric Company and comprises adding to the melt of semi-conductor material certain donors and acceptors having different segregation coefficients. It is thus possible to obtain p-n junc tions which, as experience has shown, are relatively gradual or flat and show high barrier potentials, but relatively unsatisfactory current flow properties, i.e. their resistivity is too high. This phenomenon is due to the broad character of the 13-h junction having a flat gradient, which terms shall be explained hereinafter.
A second known process for obtaining p-n junctions is that of applying to the surface of a semi-conductor body a material of opposite conductivity type and heating this material and theadjacent zone of the semi-conductor body sufficiently to cause diffusion of charged particles of the material into the semieconductor body. Again the resulting p-n junctions are broad ones, having a flat gradient from the center of the junction toward the adjacent zones of the semi-conductor body, and their properties are correspondingly very satisfactory with regard to their barrier potential, but unsatisfactory with regard to their high resistivity to heavy current loads.
The same diffusion effect may also be obtained by contacting a semi-conductor crystal with the gaseous phase of a substance imparting to the crystal an opposite conductivity type and heating so that diffusion takes place into the semi-conductor crystal directly from the gaseous phase. The resulting p-n junction sufiers from the same drawbacks as when applying a coating according to the aforesaid second known process and thus causing dilfusion by heating from a superimposed solid phase into the semi-conductor crystal.
It has been found that the barrier layer breaks down at a certain limit barrier voltage, preferably in the region where the p-n junction emerges at the crystal surface. it is believed that this is due to the fact that it is impossible to maintain this surface of the semi-conductor crystal entirely free from undesirable impurities. I have found that the narrower the 31-11 junction, the more sensitive it is against such impurities, and the more readily does it break down along the crystal surface.
In the German patent application No. 1,000,115 to K. 0. Seller issued January 3, 1957, it is already proposed to improve the resistance of p-n junctions to high barrier voltages in semi-conductor crystals in which these p-n junctions have been brought about by the abovedescribed second or diffusion method and are, therefore, of the above-darned broad character having a fiat impurity gradient. The improvement in the p-n junction is obtained by heating the semi-conductor crystal, preferably in its surface area about the p-n junction, either by a conventional tempering process or by high frequency heating.
The resulting semiconductor crystals have a flattened gradient of their p-n junction in the vicinity of the crystal surface and are said to be particularly Well suited as material for diodes.
However, since their p-n junction is usually too broad even in the interior of the semi-conductor crystal, the resulting semi-conductive system is still unsatisfactory when used as a dry plate rectifier, in particular due to the abovenientioned unsatisiactory current flow properties of broad p-n junctions.
On the other hand, it is very difiicult to control the heat diffusion effect at the surface and particularly in the interior of crystals having p-n junctions during Sei'lers tempering step. The narrower the p-n junction the more difficult is it to control this tempering step in spite of the complicated measures proposed by Seiler supra to effect a broadening of the near-surface portions of the p-n junction.
My invention avoids the above-described diificulties and draw-backs and attains the objects stated hereinbefore, by providing a new type of dry plate rectifying system and a novel process for manufacturing the same which combines the known method of obtaining narrow p-n junction having a steep gradient of impurity distribution of the opposite conductivity type, which method is known as falloying method and is, for instance, described in detail in US. Patent 2,725,315 granted to C. S. Fuller November 29, 1955, with other steps known ,per so which have also been described above.
Preferably and contrary to the methods hitherto proposed, start with a crystal having an originally broad pn junction and narrow this junction down in theinterior of the crystal in a well controlled manner, while maintaining the original breadth of the p-n junction at the surface of the crystal and in the vicinity thereof.
This simple and easily controllable method permits to obtain a semi-conductive system which combines the advantageous features of firstly excellent current flow properties in the direction of the forward current, and
a high barrier potential free from danger of causing breakdown of the p-n junction at the crystal surface.
The electrically unsymmetrically conductive system thus obtained as therefore particularly Well suited for use as a high current load rectifier system.
It is an important feature of my invention that, in a preferred embodiment of the semi-conductive system according to the same, the p-n junction is made narrow over substantially the entire extension thereof except in a relatively small marginal portion which is retained at its original breadth, so as to obtain the necessary high current flow in the direction of the forward current.
The nature of my invention will be still better understood by description thereof hereinafter in connection with the accompanying drawings, in which FIGURE 1 illustrates graphically the gradient of impurity distribution of a uniform p-n junction in a conventional semi-conductor crystal; I
FIGURE 2 illustrates in perspective and partially sectional view a semi-conductive system having a p-n junction according to the invention;
FIGURE .3 shows graphically the characteristics of the p-n junction in the interior and at the surface of the semi-conductive system of FIGURE 2;
FIGURE 4 illustrates perspectively and partly in section another embodiment of a semi-conductive system according to the invention similar to that shown in FIG- URE 2;
FIGURE 5 illustrates a dry plate rectifier comprising a semi-conductive system according to the invention;
FIGURE 6 (a to 1) illustrates, by way of example one mode of carrying out the process of making a semiconductor system according to the invention;
FIGURE 7 (a to 1) illustrates, by way of example another mode of carrying out the process of manufacturing a semi-conductor system according to the invention.
At the hand of FIGURE 1, there shall now be explained the terms of flat and steep gradient and broad and narrow p-n junction used hereinbefore.
In this figure, the semi-conductor crystal 1 consists of an n-conductivity type portion 1,, and a p-conductivity type portion 1;, which are ideally divided by the central plane I of the junction between both portions 1, and 1 A coordinate system has been placed in the longitudinal central plane of the crystal 1, with the ordinate axis being located in the plane I of the p-n junction and being subdivided in units of concentration N of impurities being either donors or acceptors, i.e. contributing to imparting either nor p-conductivity type to the crystal 1.
The abscissa is subdivided into units of length starting from the ordinate as towards both ends of crystal 1.
In the n-conductive portion of the crystal, the concentration N of donors is high while the concentration N of acceptors is low, the excess of donors determining the conductivity type of this portion as It. From a certain region, N decreases at a gradient characterized by a to a low level, while N rises at a gradient 6 to a high level, thereby reversing the conductivity type on the left, side of J, in which the concentration of acceptors now exceeds that of donors.
Obviously, the steeper angles a and 9, i.e. the gradients of concentrations of donors and acceptors, the narrower is the extension of the entire transition region a, which constitutes the p-n junction, and invertedly, the flatter these gradients, the broader is the junction.
The semi-conductive system of a dry plate rectifier illustrated schematically in'the sectional view of FIG- URE 2 comprises a semi-conductor crystal 1 which consists of an n-conductive portion 2 and a p-conductive portion 3, while the p-n junction extends between limits 4 and and emerges at the surface 1a of crystal 1 in a belt zone whose central plane intersects surface 1a as indicated at 6. In the annular portion 7 of the p-n junction 45 in the immediate vicinity of the aforesaid belt zone the gradient of the concentration of impurities of either por n-type, as the case may be, is flatter as is indicated by angles a' and B in FIGURE 3, while, in the central portion of the p-n junction which extends over almost the entire cross sectional area of the crystal 1 in the plane 6, this gradient is steeper as indicated by angles a" and ,8" in FIGURE 3-.
Consequently, in its central portion, the 13-11 junction has a diameter b, while in the marginal portions thereor, its diameter is approximately 0.
In the embodiment illustrated in FIGURE 4, the marginal zone 8 having a flat gradient of impurity concentration is nnsy'mmetrically disposed relative to the central plane 9 of the p-n junction 14) tending through the semi-conductor crystal 11,
In FIGURE 5 there isillustrated a dry plate rectifier system of the invention, which comprises a semi-conductor disc 2% of, for instance, p-type conductive germanium or silicon, an n-type semi-conductive alloy body 21 and therebetween a p-n junction which has a broad marginal portion 22 and a narrowed central portion 23.
The alloy body 21 consists of a portion of n-type germanium or silicon, containing gallium or indium or their intermetallic compounds such as gallium arsenide or indium antimonide, and/0r alloyed with lithium, or tin or gold containing, for instance, antimony or arsenic. Elements of the third group of the periodic table, other than gallium or indium, namely boron, aluminum, and thallium are also suitable for forming the alloy layer 23. with n-type or p-type germanium or silicon, as shall be described hereinafter.
The dry plate rectifier system shown in FIGURE 5 further comprises a base plate 24 of preferably molybdenum on which the semi-conductor disc 2 is mounted free from barrier layers, for instance, with a solder layer 25 of tin, or tin-antimony or tin-indium, as the case may be. Electrode 26 of aluminum is welded to the top of alloy body 21,'while electrode 27, for instance of copper, is welded to the molybdenum base plate 24.
A dry plate rectifier of this type is manufactured by the method according to the invention of which several modes are illustrated in FIGURES 6 and 7.
FIGURE 6 illustrates as a preferred mode of the method of making dry plate rectifier systems according to the invention, a step (a) of drawing from a melt of either germanium or silicon containing donor and acceptor substances, a monocrystal in which a relatively broad p-n junction is conventionally produced by changing at a determined time, the growth rate of the crystal. Thus, by altering the growth rate from, for instance, 1 millimeter per minute to 3 millimeters per minute and using gallium and arsenic or indium and antimony as impurities in the melt, the conductivity type of a drawn germanium monocrystal is changed from n-type to p type conductivity, thus leading to a monocrystal as illustrated by (b) in FIGURE 6, which crystal consists of the p-type conductivity portion 13, the n-type conductivity portion 14, and the p-n junction 15 which is relatively broad on both sides of the central plane 16 thereof.
The p-n junction is slightly curved due to the drawing process. As a next step 0 a pellet or small disc 17 is placed on top of one of the end surfaces of the monocrystal. This pellet is of a substance which imparts the same type of conductivity to the semi-conductor body, as prevails in the crystal portion on whose surface it is placed.
In FIGURE 6 (0 the pellet 17 is placed on the top surface of crystal portion 13 which is of p-type conductivity. Consequently, pellet 17 is of an element from the third group of the periodic table comprising boron (as a metaloid), and the metals aluminum, gallium, indium and thallium.
Instead of placing a pellet on portion 13, a layer of one of the aforesaid substances may be deposited on the surface of portion 13 from the vapor phase. (FIG- URE 6 (c That part of the crystal surface which is not to be coated, is preferably covered by a mask 18 (FIGURE 6 (d)).
Thereafter, as step (e) FIGURE 6, the entire system of FIGURE 6 (d) is heated in an inert atmosphere, for instance of argon or another suitable gas, during a few seconds to a temperature above 500 3. so as to melt the pellet 17 and alloy the same with the p-conductive portion 13 of the semi-conductor monocrystal. During this alloying step p-conductivity type impurities penetrate into the barrier layer zone and reduce the width of the p-n junction to a range of 1 micron and less, down to about 0.1 micron. This narrowing of the p-n junction zone is due to the alloying melting of the pconductive crystal portion 13 down into the zone of the p-n junction 15 in that part of portion 13 which lies below pellet i7. Pellet 17 and portion 13 are thus fused together to form a combined p-conductive portion 19, and a semi-conductive system as illustrated in FIG- URE 6 (f) is obtained. in this final system, the p-n junction is narrowed in its central portion 15 but broad in its marginal portion 15'.
According to a second mode of operation a given conductivity type semi-conductor crystal of silicon, germanium, or an intermetallic compound of a metal of the third subgroup with a metal of the fifth subgroup of the periodic table, is provided with a p-n junction by the heat difiusion known per se (FlGURE 7a and b). A semi-conductor block (FIGURE 70) comprising a pn junction -49, a p-conductive layer 41 and an n-conductive crystal portion 42 is then cut out of the diffusion treated semi-conductor body shown in FIGURE 76.
Subsequently, the diffusion produced p-n junction of this block is narrowed over its entire area with the exception of its marginal portions, in the same manner as is described hereinbefore in connection with FIGURES 6(c (0 etc.
A pellet is placed on that surface of the block, next to which there is located the p-n junction, and is alloyed thereto in the above-described manner, or a layer of 1a corresponding substance is vapor-deposited on that surface andheat alloyed thereto (FlGURE 7(d, e,) or 2 2))- The resulting semi-conductor system (FIGURE 7 is similar to that shown in FIGURE 6 The first described mode of ope ation (FEGURE 6(a, b, c d, e, f)) is the preferred mode because it is the best mode of controlling the final thickness of the p-n junction in the area of narrowed diameter.
My invention shall be further illustrated by a number of examples describing how the same can be carried out in practice, which examples shall, however, be considered in no way as lim-itative thereof.
Example I A monocrystal of germanium is drawn first at a growth rate of l millimeter per minute and then at 3 millimeters per minute from a melt containing germanium and, as impurity materials, gallium and arsenic. Thereby, the initially n-type conductive monocrystal changes its character to p-type conductivity. The crystal can be drawn, for instance, to a size of 9.5 m'llimeter thickness and 15 millimeters diameter.
A pellet of indium metal having a diameter of about 10 millimeters is then placed on the p-ty c germanium surface.
The system is then heated for seconds under argon to about 500 C., i.e. below the melting point of germanium (936 C.). The p-n junction, whose initial thickless is approximately 1 to 10 microns, is narrowed in the area covered by the pellet to a thickness of, for instance, about 0.8 micron or less.
it is then mounted with its n-type germanium surface on a base plate of molybdenum of a somewhat larger diameter, for instance, of millimeters, by means of ii a solder of pure tin, or and antimony, whereby formation of a barrier layer is avoided.
A copper electrode of about 8 millimeters diameter is then welded on to the molybdenum layer, and an aluminum wire of about the same diameter of 8 millimeters is welded on to the alloyed indium-p-type germanium surface of the semi-conductor system.
The dry plate rectifier thus obtained supports a current load of about 250 amperes per square centimeter and a barrier voltage of about 690 volts. 7
Comparable known semi-conductive systems comprising drawn germanium monocrystals support either barrier voltages up to 400 volts and very low current loads in the order of milliamperes up to a few amperes per Cm.' I
Dry plate rectifiers manufactured according to Example l and the following examples are particularly distinguished by their property of supporting increased pulse loads.
Example I! A germanium monocrystal of partly p-type and partly n-type conductivity and having a p--n junction intermediate these parts is prepared in the same manner as described in Example l, but mounted on the molybdenum base plate with it's p-type conductivity surface instead of its n-type conductivity side, which mounting with the p-type conductivit" surface to the molybdenum base plate is effected by means of an indium solder.
A pellet of tin containing about 8.5% of arsenic is used instead of the indium pellet described in Example 1. Otherwise, the steps of Example I are followed.
Example III A monocrystal of silicon is drawn first at a growth rate of 1.2 millimeters per minute, and then, after a given period, at the rate of 3.5 millimeters per minute from a melt containing silicon and, as impurity materials, lithium and an aluminum arsenic compound. The resulting semi-conductive crystal has a p-type conductivity portion, a 12-11 junction and an n type conductivity portion, and may be grown, for instance, to a thickness of 0.25
thick and of a diameter of 18 mm.
The crystal is then mounted with its p-side on a molybdenum base plate having a diameter of, for instance, 22 mm., with the aid of an indium tin alloy solder containing about 25% of indium.
A pellet having a diameter of about 12 mm. and consisting of tin containing about 0.5% of arsenic is then placed on the top surface of the n-type conductive silicon portion, and the system is then heated to 800 C. for about 10 seconds. The 33-12 junction is thereby narrowed in its central region to a width of about 1 micron.
An aluminum electrode is then welded to the alloyed side of the system, and a copper electrode to the molybdenum base plate. Both electrodes have diameters of about 10 mm.
The resulting electrically nnsymmetrically conductive system can be used as a dry plate rectifier which Withstands current loads of 300 amperes per cm. and a barrier voltage of about 950 volts.
Example I V A semi-conductive crystal is obtained by the steps described in Example Ill. Instead of mounting the crystal with its p-side on the molybdenum base plate, the crystal is mounted with its n-side on a molybdenum base plate having a diameter of, for instance, 22 mm, with the aid of a tin arsenic alloy solder containing about 0.5% of arsenic.
A pellet having a diameter of about 12 mm. and consisting of aluminum containing approximately 50% of indium is then placed on the top surface of the p-type conductive silicon portion. All other steps are the same as described in Example llIl.
Example V A p-type conductive germanium disc having a thickness of about 0.5 mm. and a diameter of about 14 mm., and whose resistivity is about 1 ohm centimeter is blanched and then covered with a molybdenum mask which leaves a circular surface portion of one fiat side of the disc free; the diameter of the free surface is about 11 mm. A lithium metal layer having a thickness of 0.1 mm. is then vapor deposited in vacuum on to this free portion of the disc surface.
The system is then heated in a helium atmosphere for about 10 seconds to about 700 C. whereby a p-n junction is formed at a depth of about 0.1 mm. below the lithium coated surface.
Lithium-germanium alloy which may have formed during the heating step as well as excessive lithium are then removed mechanically.
The semi-conductive system according to the invention is then produced by again covering the surface into which the p-n junction has been difiused, with a molybdenum mask having a central opening of 10 mm. diameter, and vapor depositing thereinto a layer of tin-antimony alloy containing about 0.5% of antimony, which layer is about 1.2 mm. thick.
The alloying step is then carried out by heating the system to about 500 C. for 15 seconds in an argon atmosphere. The p-n junction is narrowed in the area registering with the tin antimony deposit to a thickness below 0.8 micron.
The p-type surface of the system is soldered to a molybdenum plate by means of indium.
The system is then electrolytically blanched in a 10% kalium hydroxide solution and then rinsed in distilled water.
The system is then converted to a dry plate rectifier by further steps described in Example 1.-
Example VI 'below the lithium bearing surface.
The further treatment is similar to that described in the preceding example. mony content of about 5% is used as the alloying substance, and the alloying step is carried out during 8 seconds at a temperature of 800 C. The p-type surface is soldered to a molybdenum plate by an indium aluminum alloy containing about 50% of indium.
Example VII However, gold having an anti-' A block of n-type conductive silicon having a resistivity of about 2 ohm-cm, is blanched in a conventional manner and then heated during 16 hours at l200'C. in an inert atmosphere, for instance helium, containing about 1 percent by volume of boron triiodide B1 and having a pressure of about 300 Torr at 20 C.
The boron which is thereby heat diffused into the silicon disc, therein produces a p-n junction at a depth in the range of 0.025 cm. A disc-shaped section as illustrated in FIGURE 7b and having a thickness of 0.3 mm. is cut from the block.
In the manner described in Example V, an aluminum layer having a thickness of 0.1 mm. is then vapor deposited on the p-type conductive surface of the disc, whereupon the system is heated for about 7 seconds at 900 C. so as to alloy the aluminum and the p-type conductive boron-containing silicon.
' The system may then be treated further as described dnany one of the precedingexamples.
Intermetallic compounds such as gallium phosphide, gallium arsenide, indium antimonide and others formed between elements of the third and fifth group of the periodic table, ie between the elements Al, Ga, In, Te on the one hand and the elements P, As, Sb, Bi on the other hand may also be provided with p-n junctions in a conventional manner and then subjected to the alloying treatment according to my invention, with suitable substances, in the manner described in the preceding examples.
It Will be understood that this invention is susceptible to further modification and, accordingly, it is desired to comprehend such modifications within this invention as may fall within the scope of the appended claims.
What I claim is:
l. In the method described for producing an electrically unsymmetrically conductive system having a portion of a fusibie semi-conductive material of p-type conductivity, a portion of the same material of n-type conductivity, and a p-n junction therebetween, the steps of alloying to the outer surface of one of said portions a fusible pellet comprising substance, exhibiting the same conductivity type as that portion, said pellet being smaller in size than the area over which said p-n junction extends in said body; and of diffusing said substance into that portion of said p-n junction extending below said pellet only so as to reduce the thickness of the p-n junction below said'pellet thus eifecting only a limited area of said p-n junction.
2. A method for producing an electrically unsymmetrically conductive system comprising a body of semiconductive material of a given type conductivity selected from the group consisting of silicon, germanium and fusible intermetallic compounds, which method comp-rises the steps of (a) producing a mono-crystal semi-conductive body having a p-n junction, said p-n junction thus having a given gradient of impurity concentrations of donors and acceptors changing substantially evenly in a direction vertically to'the extension of the junction over the entire area of the latter, and (b) of causing impurities to diffuse into a central portion of said p-n junction so as to increase said gradient therein, while (0) preventing a change of said gradient in the remaining portion of said p-n junction.
3. The method producing a semi-conductor diode comprising the steps of (a) producing a semi-conductor body having two portions of opposite conductivity types and a p-n junction extending over the entire area between said portions, (12) applying to a limited surface area of one of said portions, which surface area is substantially parallel with said p-n junction, and smaller than the entire area of the latter, a material imparting to said semiconductor body the same conductivity type as that of the body portion to a surface area of which said material is being applied, and (c) heating the body and material sutficiently to alloy the latter with the body portion to which it is applied and thereby to reduce the thickness of the p-n junction in a central are-a substantially equal in extension to said limited surface area.
4. A method for producing an electrically unsymmetrically conductive system capable of supporting high current loads at high barrier voltages, comprising the steps of producing in a semi-conductor body of n-type conductivity a portion of p-type conductivity and a p-n junction between said portion of p-type conductivity and the remaining portion of said n-type body by drawing a monocrystal of silicon from a'melt containing silicon and impurity material composed of lithium and an aluminumarsenic compound and changing the growth rate thereof at a determined instant; placing a pellet of aluminum containing 50% of indium metal upon the surface of said p-type silicon portion, said pellet being smaller than said latter surface; heating said system under argon to a temperature below the melt-ing point of silicon, thus causing alloying of said indium metal and that part of said p-type silicon portion underlying said pellet of indium and causing difiusion of said indium into a central portion of said p-n junction so as to reduce the thickness of the latter in the interior of the system While retaining the original thickness of the p-n junction in the remaining portion thereof; and mounting said body with said n-type silicon surface upon a molybdenum base plate by means of a tin arsenic alloy solder containing about 0.5% of arsenic.
5. A method for producing an electrically unsymmetrically conductive system capable of supporting high current loads at high barrier voltages, comprisin the steps of blanching a block of n-type conductivity silicon, heating said block in helium containing 1% of boron triiodide thus causing the boron to be diffused into said block thereby forming a p-n junction, cutting a disc-shaped section from said block so as to expose said junction at the surface of said section, vapor depositing an aluminum layer upon a limited, circular central portion of the p-type conductivity surface of said disc while leaving uncovered a marginal portion of said p-type conductivity surface, heating said disc so as to alloy said aluminum and said p-type conductive boron-containing silicon-so as to reduce the thickness of said p-n junction in the interior of the system below said central portion while retaining the original thickness of the p-n junction where the same emerges at the surface of the system and below said marginal portion, and mounting the system with its n-type surface on a molybdenum base plate by means of a tin solder containing about 0.5% of arsenic.
6. A method of producing a semiconductor diode comprising the steps of:
(a) producing a p-n junction in imparting to a first portion a first impurity substance rendering said first portion p-type conductive and imparting to a second portion of said body, contiguous with said first portion thereof, a second impurity substance rendering said second portion n-type conductive, said p-n junction extending over the entire area between said portions;
(b) applying to a limited central surface area of a selected one of said first and second portions, a material including a third substance imparting to said selected body portion the same conductivity type as is present therein, said limited surface area being smaller than the entire surface area of said selected body portion;
(c) and causing said third substance to ditfuse into a central portion of said p-n junction so as to reduce the thickness thereof in said central portion While the thickness of the remaining portion of said p-n junction remains substantially unaffected.
7. The method of producing a semiconductor diode comprising the steps of: producing a semiconductive disc having two portions of opposite conductivity types and a p-n junction extending over the entire area between said portions; covering said disc with a mask leaving free a limited central surface area pertaining to the surface of one of said disc portions; depositing a substance on said surface area left free by said mask, said substance imparting to said disc portion to which it is applied the same type of conductivity as already present therein; and heating said disc and causing said substance to diffuse into a central portion of said p-n junction so as to reduce the thickness thereof in said central portion while the thickness of the remaining portion of said p-n junction remains substantially unaffected thereby.
References Cited in the file of this patent UNITED STATES PATENTS 2,603,693 Kircher July 15, 1952 2,665,399 Lingel Jan. 5, 1954 2,697,269 Fuller Dec. 21, 1954 2,701,326 Pfann et a1. Feb. 1, 1955 2,731,704 Spanos Jan. 24, 1956 2,751,528 Burton June 19, 1956 2,806,983 Hall Sept. 17, 1957
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US2603693A (en) * 1950-10-10 1952-07-15 Bell Telephone Labor Inc Semiconductor signal translating device
US2731704A (en) * 1952-12-27 1956-01-24 Raytheon Mfg Co Method of making transistors
US2751528A (en) * 1954-12-01 1956-06-19 Gen Electric Rectifier cell mounting
US2806983A (en) * 1956-06-01 1957-09-17 Gen Electric Remote base transistor

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3387191A (en) * 1964-04-24 1968-06-04 Int Standard Electric Corp Strain relieving transition member for contacting semiconductor devices
US3428870A (en) * 1965-07-29 1969-02-18 Gen Electric Semiconductor devices
US3697827A (en) * 1971-02-09 1972-10-10 Unitrode Corp Structure and formation of semiconductors with transverse conductivity gradients

Also Published As

Publication number Publication date
FR1176578A (en) 1959-04-13
GB861196A (en) 1961-02-15
DE1116824B (en) 1961-11-09

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